JPH05222293A - Resin composition and molding produced therefrom - Google Patents
Resin composition and molding produced therefromInfo
- Publication number
- JPH05222293A JPH05222293A JP12566091A JP12566091A JPH05222293A JP H05222293 A JPH05222293 A JP H05222293A JP 12566091 A JP12566091 A JP 12566091A JP 12566091 A JP12566091 A JP 12566091A JP H05222293 A JPH05222293 A JP H05222293A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- powder
- weight
- resin composition
- feather
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 74
- 238000000465 moulding Methods 0.000 title abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 126
- 229920005989 resin Polymers 0.000 claims abstract description 81
- 239000011347 resin Substances 0.000 claims abstract description 81
- 210000003746 feather Anatomy 0.000 claims abstract description 49
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 26
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 25
- 210000004209 hair Anatomy 0.000 claims abstract description 22
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002635 polyurethane Polymers 0.000 claims abstract description 8
- 239000004814 polyurethane Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 29
- 241001465754 Metazoa Species 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 15
- 239000002649 leather substitute Substances 0.000 abstract description 29
- 238000002156 mixing Methods 0.000 abstract description 25
- 210000002268 wool Anatomy 0.000 abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- -1 poly(amino acid) Polymers 0.000 abstract description 16
- 241000272517 Anseriformes Species 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005520 cutting process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 229920001308 poly(aminoacid) Polymers 0.000 abstract 2
- 238000010298 pulverizing process Methods 0.000 abstract 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 38
- 238000000034 method Methods 0.000 description 33
- 229920005749 polyurethane resin Polymers 0.000 description 28
- 239000007787 solid Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 22
- 230000035699 permeability Effects 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 239000010985 leather Substances 0.000 description 16
- 238000012545 processing Methods 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 14
- 229920003002 synthetic resin Polymers 0.000 description 14
- 239000000057 synthetic resin Substances 0.000 description 14
- 102000008186 Collagen Human genes 0.000 description 12
- 108010035532 Collagen Proteins 0.000 description 12
- 229920001436 collagen Polymers 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920001194 natural rubber Polymers 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 241000271566 Aves Species 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 241000272814 Anser sp. Species 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 241000282832 Camelidae Species 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 2
- 241000283707 Capra Species 0.000 description 2
- 241000272201 Columbiformes Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 102000009123 Fibrin Human genes 0.000 description 2
- 108010073385 Fibrin Proteins 0.000 description 2
- BWGVNKXGVNDBDI-UHFFFAOYSA-N Fibrin monomer Chemical compound CNC(=O)CNC(=O)CN BWGVNKXGVNDBDI-UHFFFAOYSA-N 0.000 description 2
- 241000287828 Gallus gallus Species 0.000 description 2
- 241000283973 Oryctolagus cuniculus Species 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 241000271567 Struthioniformes Species 0.000 description 2
- 241001416177 Vicugna pacos Species 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 235000009120 camo Nutrition 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 235000005607 chanvre indien Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000013330 chicken meat Nutrition 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229950003499 fibrin Drugs 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011487 hemp Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 244000144977 poultry Species 0.000 description 2
- 235000013594 poultry meat Nutrition 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【産業上の利用分野】本発明は樹脂組成物及びそれを用
いた成形品に係わり、詳しく述べると合成皮革、人工皮
革、透湿性防水布帛等の合成シート、立体成形品、糸等
の成形品の製造に、または塗料等のコーティング剤とし
て用いる際に該合成樹脂の特性を損なわずに、優れた透
湿性、漆黒性、耐スクラッチ性及びドライタッチでスエ
ード調の風合いを付与する有用な樹脂組成物及びそれを
用いた成形品に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition and a molded article using the same, and more specifically, synthetic leather, artificial leather, synthetic sheets such as moisture-permeable waterproof cloth, three-dimensional molded articles, molded articles such as threads. A useful resin composition for imparting a suede-like texture with excellent moisture permeability, jet blackness, scratch resistance and dry touch, without impairing the properties of the synthetic resin when it is used for the production of or as a coating agent for paints and the like. The present invention relates to a product and a molded product using the product.
【従来の技術】合成皮革、人工皮革、金属、プラスチッ
ク、セラミックス、木材等の表面をスエード調触感に仕
上げるための表面処理剤は従来から種々開発されてい
る。代表的なものとしては（１）ポリウレタン樹脂溶液
に脂肪酸エステル、シリカを配合したもの、（２）ポリ
ウレタン樹脂溶液、アクリル樹脂溶液にジメチルポリシ
ロキサン、シリカを配合したもの、（３）ポリウレタン
樹脂溶液にポリエチレン微粉末、ポリブチレン微粉末、
アクリル樹脂微粉末、ウレタン樹脂微粉末、ナイロン樹
脂微粉末あるいはシリコン樹脂微粉末等の１種とシリカ
を配合したもの、等がある。しかし、これらの処理剤で
合成皮革、例えばポリ塩化ビニルレザー（以下、ＰＶＣ
レザーという）や合成樹脂成形品等をグラビアプリンタ
ー法、スプレー法等により表面処理して形成した被覆層
表面は爪で引っかくことにより容易に破壊、変形すると
いう現象が見られ、耐スクラッチ性に欠け、また手で触
れた部分は指紋等が残る、あるいはべた付き感がある等
の問題がある。また、ポリウレタン樹脂、アクリル樹
脂、ナイロン樹脂等の粉体をポリイソシアネート類と共
にウレタン樹脂有機溶媒溶液中で調合し、スプレー処理
する方法も提案されているが、風合い、ポットライフ、
焼付け温度等の問題がある。一方、透湿性を付与する方
法も種々開発されており、代表的なものとしては（４）
ポリウレタン樹脂溶液ポリアミノ酸ウレタン樹脂溶液
等を用いて多孔質合成シートとする方法、（５）ポリウ
レタン樹脂溶液等にゼラチン微粒子、またはゼラチン微
粒子と微細粉状の革粉を含有させて被膜を形成させ、温
水でゼラチン粒子を一部溶出させる方法（特開平１−２
２２９３８、特開平１−２２２９３９）、等がある。し
かし、（４）の方法については、被膜を極薄状にする必
要があるため耐摩耗性が悪く、またそれ自体において吸
湿機能が小さいため、接触時にべた付き感が生ずるとい
う問題点がある。また、（５）の方法については、工程
が煩雑であり、樹脂に対する分散性が悪く、漆黒性、風
合いがやや劣るという問題点がある。2. Description of the Related Art Various surface treatment agents for finishing the surface of synthetic leather, artificial leather, metal, plastic, ceramics, wood, etc. to a suede-like feel have been developed. Typical examples include (1) polyurethane resin solution mixed with fatty acid ester and silica, (2) polyurethane resin solution, acrylic resin solution mixed with dimethylpolysiloxane, silica, and (3) polyurethane resin solution. Polyethylene fine powder, polybutylene fine powder,
One of acrylic resin fine powder, urethane resin fine powder, nylon resin fine powder, silicon resin fine powder, and the like, and a mixture of silica and the like are available. However, with these treatment agents, synthetic leather such as polyvinyl chloride leather (hereinafter referred to as PVC
There is a phenomenon that the surface of the coating layer formed by surface treatment of leather) and synthetic resin molded products by gravure printer method, spray method, etc. is easily broken and deformed by scratching with nails, and scratch resistance is lacking. Also, there is a problem that fingerprints and the like remain on the part that is touched with the hand, or there is a sticky feeling. In addition, a method of preparing a powder of polyurethane resin, acrylic resin, nylon resin or the like in a urethane resin organic solvent solution together with polyisocyanates and spraying it is also proposed, but the texture, pot life,
There are problems such as baking temperature. On the other hand, various methods for imparting moisture permeability have been developed, and typical methods include (4)
Polyurethane resin solution A method of forming a porous synthetic sheet using a polyamino acid urethane resin solution or the like, (5) A fine particle-like leather powder or gelatin fine particles is added to the polyurethane resin solution or the like to form a film, A method in which gelatin particles are partially eluted with warm water (JP-A 1-2
22938, JP-A-1-222939), and the like. However, with the method (4), there is a problem that abrasion resistance is poor because it is necessary to make the coating film extremely thin, and the moisture absorption function itself is small, so that a sticky feeling occurs at the time of contact. Further, the method (5) has the problems that the process is complicated, the dispersibility in the resin is poor, and the jet-blackness and the texture are slightly inferior.
【発明が解決しようとする課題】本発明は、上述の問題
に鑑みて行われたもので、優れた透湿性、耐スクラッチ
性、および柔らかくドライタッチでべた付き感がなく、
スエード調の風合いを有する分散性のよい合成樹脂組成
物およびこれを加工して得られる成形品を得ることを目
的とするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has excellent moisture permeability, scratch resistance, and softness and dry touch without stickiness.
It is intended to obtain a synthetic resin composition having a suede-like texture and good dispersibility, and a molded article obtained by processing the synthetic resin composition.
【課題を解決するための手段】本発明者は、かかる問題
を解決するために各種合成樹脂について鋭意研究を行っ
た結果、合成樹脂に獣毛粉末及び／または羽毛粉末を含
有させることにより、好適な特性を損なわずに優れた透
湿性、耐スクラッチ性、漆黒性および柔らかくドライタ
ッチでべた付き感がなく、スエード調の風合いを有する
分散性のよい樹脂組成物が得られることを見いだし、本
発明を完成するに至ったものである。即ち、本発明は合
成樹脂１００重量部に対して獣毛粉末及び／または羽毛
粉末を１〜１００重量部含有することを特徴とする樹脂
組成物及び該樹脂組成物からなるまたは該樹脂組成物が
基材にコートされている成形品に関する。以下、本発明
を詳細に説明する。本発明で用いられる樹脂としては種
類を問わずいずれのものでも使用でき、例えばポリアミ
ノ酸、ポリアミノ酸ウレタン、ポリアミド、ポリウレタ
ン、ポリエステル、ポリエステルアミド、アクリロニト
リル系重合体、ポリ塩化ビニル、ポリスチレン及びその
共重合体、ポリビニルアルコール及びその誘導体、ポリ
酢酸ビニル及びその共重合体、ポリアクリルアミドまた
はポリメタクリルアミド及びこれらの誘導体、天然ゴム
及びポリイソプレン、ポリブタジエンなどの合成ゴム並
びにこれらの混合物、ボリエチレン及びその共重合体、
ポリプレン及びその共重合体、フェノール樹脂、メラミ
ン樹脂、尿素樹脂等の１種または２種以上の混合物が挙
げられ、必要に応じて溶剤で希釈して用いることが出来
る。これらの中ではポリウレタン、ポリアミノ酸ウレタ
ン及びポリ塩化ビニルが獣毛粉末及び羽毛粉末の樹脂へ
の分散性及び成形品とした場合の風合い、耐スクラッチ
性等の理由から好ましい。本発明でいう獣毛粉末とは
羊、山羊、兎、ラクダ、アルパカ等の動物より得られる
獣毛（天然ケラチン質繊維）を粉砕したものを意味し、
平均粒径は８０ミクロン以下が好ましく、さらに好まし
くは１０ミクロン以下である。平均粒径が８０ミクロン
より大きいと加工して得られる成形品にざらつき感が生
じ、風合い上好ましくない。本発明でいう羽毛粉末とは
鶏、あひる、がちょう等の家禽、鴨等の水鳥、鳩、ダチ
ョウ等の鳥類より得られる羽毛（天然ケラチン質繊維）
を粉砕したものを意味し、平均粒径は８０ミクロン以上
が好ましく、さらに好ましくは１０ミクロン以下であ
る。平均粒径が８０ミクロンより大きいと加工して得ら
れる成形品にざらつき感が生じ、風合い上好ましくな
い。獣毛粉末および羽毛粉末はそれぞれ単用してもよく
また併用してもよいが、これらの樹脂に対する添加量の
合計は樹脂１００重量部に対して１〜１００重量部、好
ましくは５〜３０重量部である。添加量が１重量部未満
だと透湿性、及びスエード調の風合いが不充分であり、
１００重量部より多いと樹脂に対する分散が困難であ
り、また耐摩耗性、剥離強度、風合い等が低下し好まし
くない。なお、獣毛粉末及び／または羽毛粉末と他のフ
ィラーを併用して樹脂に添加して用いてもなんら差し支
えない。獣毛粉末及び羽毛粉末を樹脂に分散含有させる
方法は用いる樹脂により適宜選択でき、ディスパー分
散、アトマイザー、ダイモミル、ボールミル、三本ロー
ル、万能混合機による混練り等が挙げられる。本発明の
樹脂組成物は成形品の基材として、また塗料、コーティ
ング剤等の用途で用いることができる。本発明の樹脂組
成物からなる成形品は合成シート、、立体成形品、糸等
の形状であり、合成シートとしては合成皮革、人工皮
革、フィルム、板、弾性体等が挙げられる。樹脂組成物
の成形法としては圧縮成形、トランスファー成形、射出
成形、積層成形、押出成形、カレンダー成形等が挙げら
れ、樹脂に応じて適宜選択できる。また、本発明の樹脂
組成物が基材にコートされている成形品の場合の、コー
ティングする成形物に用いることの出来る基材として
は、例えば綿、麻、パルプ、木材、竹、ビスコース人
絹、ベンベルグ人絹、セルロースアセテート等の繊維素
及びその誘導体、絹、羊毛、天然皮革、再生皮革、合成
皮革、人工皮革、ポリアミノ酸、ポリアミノ酸ウレタ
ン、ポリアミド、ポリウレタン、ポリエステル、ポリエ
ステルアミド、アクリロニトリル系重合体、ポリ塩化ビ
ニル、ポリスチレン及びその共重合体、ポリビニルアル
コール及びその誘導体、ポリ酢酸ビニル及びその共重合
体、ポリアクリルアミド及びポリメタクリルアミド並び
にこれらの誘導体、天然ゴム及びポリイソプレン、ポリ
ブタジエン等の合成ゴム並びにこれらの混合物、ポリエ
チレン及びのその共重合体、ポリプロピレン及びその共
重合体、フェノール樹脂、メラミン樹脂、尿素樹脂等の
各種プラスチックス、石英、ガラス、セラミックス、セ
メント類、各種金属類等の１種または２種以上の混合材
が挙げられる。これらの基材による成形品としては、例
えば、布帛、合成皮革、人工皮革、フィルム、紙類、
板、ゴム、プラスチック等のシート状成形品や自動車等
のプラスチック製ハンドル等が挙げられる。また、これ
らの基材による成形品に獣毛粉末及び／または羽毛粉末
を樹脂に添加した本発明の樹脂組成物を塗布による加
工、浸漬による加工、スプレー加工、グラビア加工等を
行うことにより加工することができ、また乾式法で離型
紙上にフィルム化して上記基材とラミネート加工等によ
り表皮材として用いることが出来る。すなわち、加工法
そのものは従来法によることができる。Means for Solving the Problems As a result of earnest studies on various synthetic resins in order to solve the above problems, the present inventors have found that it is preferable that the synthetic resin contains animal hair powder and / or feather powder. It has been found that a resin composition having excellent moisture permeability, scratch resistance, jet blackness, and soft and dry touch without sticking, and having a good dispersibility and having a suede-like texture can be obtained without impairing the characteristics of the present invention. Has been completed. That is, the present invention comprises a resin composition comprising 1 to 100 parts by weight of animal hair powder and / or feather powder with respect to 100 parts by weight of a synthetic resin, and the resin composition or the resin composition. The present invention relates to a molded article coated on a base material. Hereinafter, the present invention will be described in detail. As the resin used in the present invention, any resin can be used regardless of the type, and examples thereof include polyamino acid, polyamino acid urethane, polyamide, polyurethane, polyester, polyesteramide, acrylonitrile polymer, polyvinyl chloride, polystyrene and its copolymerization weight. Polymers, polyvinyl alcohol and derivatives thereof, polyvinyl acetate and copolymers thereof, polyacrylamide or polymethacrylamide and derivatives thereof, natural rubber and synthetic rubbers such as polyisoprene and polybutadiene, and mixtures thereof, polyethylene and copolymers thereof. ,
Examples thereof include one or a mixture of two or more of polyprene and its copolymer, phenol resin, melamine resin, urea resin and the like, and they can be used after diluting with a solvent as necessary. Among these, polyurethane, polyamino acid urethane and polyvinyl chloride are preferable from the viewpoints of dispersibility of animal hair powder and feather powder in resin, texture when formed into a molded product, scratch resistance and the like. The animal hair powder referred to in the present invention means crushed animal hair (natural keratinous fiber) obtained from animals such as sheep, goats, rabbits, camels and alpaca,
The average particle size is preferably 80 microns or less, more preferably 10 microns or less. If the average particle size is larger than 80 microns, the molded product obtained by processing will be rough, which is not preferable in terms of texture. The feather powder referred to in the present invention is a feather (natural keratinous fiber) obtained from poultry such as chickens, ducks, and gooses, water birds such as ducks, birds such as pigeons and ostriches.
Is ground, and the average particle size is preferably 80 microns or more, more preferably 10 microns or less. If the average particle size is larger than 80 microns, the molded product obtained by processing will be rough, which is not preferable in terms of texture. Animal hair powder and feather powder may be used individually or in combination, but the total amount of addition to these resins is 1 to 100 parts by weight, preferably 5 to 30 parts by weight, relative to 100 parts by weight of the resin. It is a department. If the amount added is less than 1 part by weight, moisture permeability and suede-like texture are insufficient,
If it is more than 100 parts by weight, it is difficult to disperse it in the resin, and abrasion resistance, peeling strength, texture and the like are deteriorated, which is not preferable. It should be noted that animal hair powder and / or feather powder and other filler may be used in combination and added to the resin without any problem. The method of dispersing and containing animal hair powder and feather powder in the resin can be appropriately selected depending on the resin used, and examples thereof include disperser dispersion, atomizer, dimmo mill, ball mill, three rolls, and kneading with a universal mixer. The resin composition of the present invention can be used as a base material for molded articles and for applications such as paints and coating agents. The molded product made of the resin composition of the present invention has a shape such as a synthetic sheet, a three-dimensional molded product, and a thread. Examples of the synthetic sheet include synthetic leather, artificial leather, a film, a plate, and an elastic body. Examples of the molding method of the resin composition include compression molding, transfer molding, injection molding, lamination molding, extrusion molding, calender molding, and the like, which can be appropriately selected depending on the resin. Further, in the case of a molded article in which the resin composition of the present invention is coated on a substrate, examples of the substrate that can be used for the molded article to be coated include cotton, hemp, pulp, wood, bamboo, and viscose. Silk, Bemberg silk, fibrin such as cellulose acetate and its derivatives, silk, wool, natural leather, regenerated leather, synthetic leather, artificial leather, polyamino acid, polyamino acid urethane, polyamide, polyurethane, polyester, polyesteramide, acrylonitrile series Synthesis of polymers, polyvinyl chloride, polystyrene and its copolymers, polyvinyl alcohol and its derivatives, polyvinyl acetate and its copolymers, polyacrylamide and polymethacrylamide and their derivatives, natural rubber and polyisoprene, polybutadiene, etc. Rubber and mixtures thereof, polyethylene And their copolymers, polypropylene and their copolymers, various plastics such as phenolic resin, melamine resin, urea resin, quartz, glass, ceramics, cements, various metals and the like, or a mixture of two or more thereof. There are materials. Examples of molded articles made of these base materials include cloth, synthetic leather, artificial leather, films, papers,
Examples include sheet-shaped molded products such as plates, rubber and plastics, and plastic handles such as automobiles. In addition, processing is performed by applying processing, dipping processing, spray processing, gravure processing, etc. to the resin composition of the present invention in which animal hair powder and / or feather powder is added to the resin in a molded product of these base materials. Alternatively, it can be formed into a film on a release paper by a dry method and used as a skin material by laminating with the above base material. That is, the processing method itself can be the conventional method.
【実施例】以下、実施例により本発明をさらに詳しく説
明する。 実施例１ 羊毛粉末の製法 １，１，１−トリクロロエタンにより充分脱脂後の羊毛
をカッターにより数ミリ長のチップとなした脱脂チップ
１ｋｇを０．１Ｎ水酸化ナトリウム水溶液５リットルを
加えて常圧、８０℃にて３０分間撹拌しながら部分加水
分散処理した。これを濾過し、水中に再分散させ、塩酸
溶液で中和、洗浄後、セラミックス製ボールミルにて２
４時間湿式法により微粒子化した。これを遠沈処理後、
乾燥し、平均粒径５〜１０ミクロンの羊毛粉末９００ｇ
を得た。 実施例２ 羽毛粉末の製法 実施例１におけると同様に処理した水鳥（がちょう）の
羽毛チップ１ｋｇを０．１Ｎ水酸化ナトリウム水溶液５
リットルに分散させ、１０リットル容の加圧容器にて１
２０℃で３０分間攪拌しながら部分加水分解した。以
下、再び実施例１におけると同様に処理して平均粒径５
〜１０ミクロンの羽毛微細粉末９２０ｇを得た。 実施例３ ポリウレタン樹脂溶液と羊毛粉末との配合 ポリウレタン樹脂溶液（セイコー化成（株）製「ラック
スキン５００５」）に、その樹脂固形分１００重量部に
対して実施例１で得た羊毛粉末を５，３０及び１００重
量部添加し、ディスパー撹拌して均一に分散させた後、
脱泡を行い、３種の樹脂組成物Ａ１，Ｂ１及びＣ１を得
た。樹脂組成物Ａ１，Ｂ１及びＣ１における羊毛粉末の
分散性はいずれも良好であった。 実施例４ ポリアミノ酸ウレタン樹脂溶液と羊毛粉末と
の配合 ポリアミノ酸ウレタン樹脂溶液（セイコー化成（株）製
「ラックスキンＡ３５７１」）に、その樹脂固形分１０
０重量部に対して実施例１で得た羊毛粉末を５，３０及
び１００重量部添加し、ディスパー撹拌して均一に分散
させた後、脱泡を行い、樹脂組成物Ｄ１，Ｅ１及びＦ１
を得た。樹脂組成物Ｄ１，Ｅ１及びＦ１における羊毛粉
末の分散性はいずれも良好であった。 実施例５ 塩化ビニル樹脂溶液と羊毛粉末との配合 ポリ塩化ビニル樹脂溶液（セイコー化成（株）製「ラッ
クスキン３０１）に、その樹脂固形分１００重量部に対
して実施例１で得た羊毛粉末を５，３０及び１００重量
部添加し、３本ロールで均一に分散させた後、脱泡を行
い、樹脂組成物Ｇ１，Ｈ１及び１１を得た。樹脂組成物
Ｇ１，Ｈ１及びＩ１における羊毛粉末の分散性はいずれ
も良好であった。 実施例６ ポリウレタン樹脂溶液と羽毛粉末との配合 ポリウレタン樹脂溶液（セイコー化成（株）製「ラック
スキン５００５」）に、その樹脂固形分１００重量部に
対して実施例２で得た羽毛粉末を５，３０及び１００重
量部添加し、ディスパー撹拌して均一に分散させた後、
脱泡を行い、樹脂組成物Ａ２，Ｂ２，及びＣ２を得た。
樹脂組成物Ａ２，Ｂ２及びＣ２における羽毛粉末の分散
性はいずれも良好であった。 実施例７ ポリアミノ酸ウレタン樹脂溶液と羽毛粉末と
の配合 ポリアミノ酸ウレタン樹脂溶液（セイコー化成（株）製
「ラックスキンＡ３５７１」）に、その樹脂固形分１０
０重量部に対して実施例２で得た羽毛粉末を５，３０及
び１００重量部添加し、ディスパー撹拌して均一に分散
させた後、脱泡を行い、樹脂組成物Ｄ２，Ｅ２及びＦ２
を得た。樹脂組成物Ｄ２，Ｅ２及びＦ３における羽毛粉
末分の散性はいずれも良好であった。 実施例８ ポリ塩化ビニル樹脂溶液と羽毛粉末との配合 ポリ塩化ビニル樹脂溶液（セイコー化成（株）製「ラッ
クスキン３０１」）に、その樹脂固形分１００重量部に
対して実施例２で得た羽毛粉末を５，３０及び１００重
量部添加し、３本ロールで均一に分散させた後、脱泡を
行い、樹脂組成物Ｇ２，Ｈ２及びＩ２を得た。樹脂組成
物Ｇ２，Ｈ２及びＩ２における羽毛粉末の分散性はいず
れも良好であった。 比較例１ ポリウレタン樹脂溶液とコラーゲン粉末との
配合 ポリウレタン樹脂溶液（セイコー化成（株）製「ラック
スキン５００５」）１００重量部に粉砕したコラーゲン
粉末（昭和電工（株）製「ＣＸ−２４０−１」）を樹脂
固形分に対して５，３０及び１００重量部添加し、３本
ロールで均一に分散させた後、脱泡を行い、樹脂組成物
Ｊ１，Ｋ１及びＬ１を得た。 比較例２ ポリウレタン樹脂溶液とシリカ粉末との配合 ポリウレタン樹脂溶液（セイコー化成（株）製「ラック
スキン５００５」）１００重量部に粉砕したシリカ粉末
（デグサジャパン（株）製「ＯＫ−４１２」）を樹脂固
形分に対して５，３０及び１００重量部添加し、３本ロ
ールで均一に分散させた後、脱泡を行い、樹脂組成物Ｊ
２，Ｋ２及びＬ２を得た。 比較例３ ポリアミノ酸ウレタン樹脂溶液とコラーゲン
粉末との配合 ポリアミノ酸ウレタン樹脂溶液（セイコー化成（株）製
「ラックスキンＡ３５７１」）１００重量部に粉砕した
コラーゲン粉末（昭和電工（株）製「ＣＸ−２４０−
１」）を樹脂固形分に対して５，３０及び１００重量部
添加し、３本ロールで均一に分散させた後、脱泡を行
い、樹脂組成物Ｍ１，Ｎ１，及びＰ１を得た。 比較例４ ポリアミノ酸ウレタン樹脂溶液とシリカ粉末
との配合 ポリアミノ酸ウレタン樹脂溶液（セイコー化成（株）製
「ラックスキンＡ３５７１） １００重量部に粉砕した
シリカ粉末（デグサジャパン（株）製「ＯＫ−４１
２」）を樹脂固形分に対して５，３０及び１００重量部
添加し、３本ロールで均一に分散させた後、脱泡を行
い、樹脂組成物Ｍ２，Ｎ２及びＰ２を得た。 比較例５ ポリ塩化ビニル樹脂溶液とコラーゲン粉末と
の配合 ポリ塩化ビニル樹脂溶液（セイコー化成（株）製「ラッ
クスキン３０１」）１００重量部に粉砕したコラーゲン
粉末（昭和電工（株）製「ＣＸ−２４０−１」）を樹脂
固形分に対して５，３０及び１００重量部添加し、３本
ロールで均一に分散させた後、脱泡を行い、樹脂組成物
Ｑ１，Ｒ１及びＳ１を得た。 比較例６ ポリ塩化ビニル樹脂溶液とシリカ粉末との配
合 ポリ塩化ビニル樹脂溶液（セイコー化成（株）製「ラッ
クスキン３０１」）１００重量部に粉砕したシリカ粉末
（デグサジャパン（株）製「ＯＫ−４１２」）を樹脂固
形分に対して５，３０及び１００重量部添加し、３本ロ
ールで均一に分散させた後、脱泡を行い、樹脂組成物Ｑ
２，Ｒ２及びＳ２を得た。 検査例１ 透湿度及びスエード調外観の評価 実施例３〜８及び比較例１〜６で得た樹脂組成物及び粉
末無添加の樹脂溶液をそれぞれ離型紙上に溶剤除去後の
厚さが２０ミクロンとなるようにロールコーターで塗布
し、８０℃で５分間、１２０℃で１０分間乾燥して評価
用膜とし、透湿度およびスエード調外観の評価を行っ
た。なお、評価基準は次の通りである。 （１）透湿度 ＪＩＳ Ｌ １０９９（塩化カルシウム
法）に準じた。 （２） スエード調外観 目視により以下の基準で判定
した。 ○ 天然皮革に酷似している。 △ 天然皮革にやや似ている。 × 天然皮革の感じがない。 結果を表１〜３に示す。表１〜３より、本発明により得
られたシートは透湿度及びスエード調外観ともに優れて
いることは明らかである。EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 Method for producing wool powder 1 kg of defatted chips obtained by cutting the wool sufficiently degreased with 1,1,1-trichloroethane into chips of several millimeters by a cutter, and adding 5 liters of 0.1N sodium hydroxide aqueous solution at normal pressure, A partial hydrolysis-dispersion treatment was carried out while stirring at 80 ° C. for 30 minutes. This is filtered, redispersed in water, neutralized with a hydrochloric acid solution, washed, and then 2 with a ceramic ball mill.
Fine particles were formed by a wet method for 4 hours. After centrifuging this,
900 g of dried wool powder with an average particle size of 5-10 microns
Got Example 2 Manufacturing method of feather powder 1 kg of feather tips of waterfowl treated in the same manner as in Example 1 was treated with 0.1N sodium hydroxide aqueous solution 5
Disperse in 1 liter and press in a 10 liter pressurized container to
Partial hydrolysis was carried out with stirring at 20 ° C. for 30 minutes. Thereafter, the same treatment as in Example 1 is performed again to obtain an average particle size of 5
920 g of -10 micron feather fine powder were obtained. Example 3 Blending of Polyurethane Resin Solution with Wool Powder A polyurethane resin solution (“Luck Skin 5005” manufactured by Seiko Kasei Co., Ltd.) was mixed with 5 parts of the wool powder obtained in Example 1 per 100 parts by weight of the resin solid content. , 30 and 100 parts by weight were added, and the mixture was dispersed by stirring with a disper,
Defoaming was performed to obtain three kinds of resin compositions A1, B1 and C1. The dispersibility of the wool powder in each of the resin compositions A1, B1 and C1 was good. Example 4 Blending of Polyamino Acid Urethane Resin Solution and Wool Powder A polyamino acid urethane resin solution (“Lack Skin A3571” manufactured by Seiko Kasei Co., Ltd.) was used, and the resin solid content was 10%.
5, 30 and 100 parts by weight of the wool powder obtained in Example 1 was added to 0 parts by weight, and the mixture was stirred with a disper and uniformly dispersed, followed by defoaming to obtain resin compositions D1, E1 and F1.
Got The dispersibility of the wool powder in each of the resin compositions D1, E1 and F1 was good. Example 5 Blending of Vinyl Chloride Resin Solution and Wool Powder A polyvinyl chloride resin solution (“Lack Skin 301” manufactured by Seiko Kasei Co., Ltd.) was mixed with 100% by weight of the resin solid content of the wool powder obtained in Example 1. 5, 30 and 100 parts by weight were added, and the mixture was uniformly dispersed with a three-roll mill, followed by defoaming to obtain resin compositions G1, H1 and 11. Wool powder in resin compositions G1, H1 and I1. Example 6 Blending of Polyurethane Resin Solution and Feather Powder A polyurethane resin solution (“Lack Skin 5005” manufactured by Seiko Kasei Co., Ltd.) was added to 100 parts by weight of the resin solid content. Then, 5, 30 and 100 parts by weight of the feather powder obtained in Example 2 were added, and the mixture was dispersed by stirring with a disper,
Defoaming was performed to obtain resin compositions A2, B2, and C2.
The dispersibility of the feather powder in each of the resin compositions A2, B2 and C2 was good. Example 7 Blending of Polyamino Acid Urethane Resin Solution and Feather Powder A polyamino acid urethane resin solution (“Lack Skin A3571” manufactured by Seiko Kasei Co., Ltd.) was used, and the resin solid content was 10%.
5, 30 and 100 parts by weight of the feather powder obtained in Example 2 was added to 0 part by weight, and the mixture was uniformly dispersed by stirring with a disper and then defoamed to obtain resin compositions D2, E2 and F2.
Got In the resin compositions D2, E2 and F3, the dispersibility of the feather powder component was good. Example 8 Blending of Polyvinyl Chloride Resin Solution and Feather Powder A polyvinyl chloride resin solution (“Luck Skin 301” manufactured by Seiko Kasei KK) was obtained in Example 2 with respect to 100 parts by weight of the resin solid content. Feather powder was added in an amount of 5, 30 and 100 parts by weight and uniformly dispersed by a three-roll mill, followed by defoaming to obtain resin compositions G2, H2 and I2. The dispersibility of the feather powder in each of the resin compositions G2, H2 and I2 was good. Comparative Example 1 Blending of Polyurethane Resin Solution and Collagen Powder Collagen powder pulverized into 100 parts by weight of polyurethane resin solution (“Lackskin 5005” manufactured by Seiko Kasei Co., Ltd. “CX-240-1” manufactured by Showa Denko KK) 5, 30 and 100 parts by weight relative to the resin solid content was added and uniformly dispersed with a three-roll mill, followed by defoaming to obtain resin compositions J1, K1 and L1. Comparative Example 2 Blending of Polyurethane Resin Solution and Silica Powder 100 parts by weight of a polyurethane resin solution (“Luckskin 5005” manufactured by Seiko Kasei Co., Ltd.) was pulverized into silica powder (“OK-412” manufactured by Degussa Japan Co., Ltd.). Resin composition J was added after adding 5, 30 and 100 parts by weight to the resin solid content and uniformly dispersing with a three-roll.
2, K2 and L2 were obtained. Comparative Example 3 Blending of Polyamino Acid Urethane Resin Solution and Collagen Powder Collagen powder pulverized into 100 parts by weight of polyamino acid urethane resin solution (“Luck Skin A3571” manufactured by Seiko Kasei Co., Ltd., “CX-manufactured by Showa Denko KK”) 240-
1 ") was added to the resin solid content in an amount of 5, 30 and 100 parts by weight and uniformly dispersed with a three-roll mill, followed by defoaming to obtain resin compositions M1, N1 and P1. Comparative Example 4 Blending of Polyamino Acid Urethane Resin Solution and Silica Powder Polyamino acid urethane resin solution (“Luck Skin A3571” manufactured by Seiko Kasei Co., Ltd.) 100 parts by weight of silica powder (“OK-41” manufactured by Degussa Japan Co., Ltd.)
2 ") was added to the resin solid content in an amount of 5, 30 and 100 parts by weight and uniformly dispersed by a three-roll mill, followed by defoaming to obtain resin compositions M2, N2 and P2. Comparative Example 5 Blending of Polyvinyl Chloride Resin Solution and Collagen Powder Collagen powder pulverized into 100 parts by weight of polyvinyl chloride resin solution (“Lack Skin 301” manufactured by Seiko Kasei Co., Ltd., “CX-manufactured by Showa Denko KK”) 240-1 ") was added in an amount of 5, 30 and 100 parts by weight with respect to the resin solid content and uniformly dispersed with a three-roll mill, followed by defoaming to obtain resin compositions Q1, R1 and S1. Comparative Example 6 Blending of Polyvinyl Chloride Resin Solution and Silica Powder Polyvinyl chloride resin solution (“Luck Skin 301” manufactured by Seiko Kasei Co., Ltd.) 100 parts by weight of silica powder (“OK-” manufactured by Degussa Japan Co., Ltd.) 412 ") is added to the resin solid content in an amount of 5, 30 and 100 parts by weight and uniformly dispersed by a three-roll mill, followed by defoaming to obtain a resin composition Q.
2, R2 and S2 were obtained. Inspection Example 1 Evaluation of Water Vapor Permeability and Suede-Like Appearance The resin compositions obtained in Examples 3 to 8 and Comparative Examples 1 to 6 and the resin solution containing no powder are each 20 μm in thickness after removing the solvent on the release paper. Was applied by a roll coater so as to obtain a film for evaluation by drying at 80 ° C. for 5 minutes and 120 ° C. for 10 minutes, and the moisture permeability and the suede-like appearance were evaluated. The evaluation criteria are as follows. (1) Water vapor transmission rate According to JIS L 1099 (calcium chloride method). (2) Suede-like appearance The appearance was visually evaluated according to the following criteria. ○ It is very similar to natural leather. △ Slightly similar to natural leather. × There is no feeling of natural leather. The results are shown in Tables 1-3. From Tables 1 to 3, it is clear that the sheet obtained according to the present invention is excellent in both moisture permeability and suede appearance.
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 検査例２ 漆黒性及び耐スクラッチ性の評価 実施例３〜８及び比較例１〜６で得た樹脂組成物及び粉
末無添加の樹脂溶液を黒色ＡＢＳシートにグラビヤプリ
ンターを用いて３０ｇ／ｍ２塗工し、１２０℃で５分間
乾燥して表面仕上げして評価用シートとし、漆黒性及び
耐スクラッチ性の評価を行った。なお、評価基準は次の
通りである。 （３）漆黒性 目視により以下の基準で判定した。 ○ 黒さが充分である。 △ 黒さがやや欠ける。 × 黒さが欠ける。 （４）耐スクラッチ性 硬度Ｈの鉛筆で表面をこすり、
目視により以下の基準で判定した。 ○ 異常なし。 △ 引きかき傷ややあり。 × 引きかき傷大。 結果を表４〜６に示す。表４〜６より、本発明により得
られたシートは漆黒性及び耐スクラッチ性ともに優れて
いることは明らかである。[Table 3] Inspection Example 2 Evaluation of jet blackness and scratch resistance The resin compositions obtained in Examples 3 to 8 and Comparative Examples 1 to 6 and the resin solution containing no powder were coated on a black ABS sheet at 30 g / m 2 using a gravure printer. The sheet was processed, dried at 120 ° C. for 5 minutes and surface-finished to give an evaluation sheet, and the jet blackness and scratch resistance were evaluated. The evaluation criteria are as follows. (3) Jetness Blackness was visually evaluated according to the following criteria. ○ Black is sufficient. △ Black is slightly lacking. × Black is missing. (4) Scratch resistance Rubbing the surface with a pencil of hardness H,
It was judged visually by the following criteria. ○ No abnormality. △ Some scratches. × Large scratches. The results are shown in Tables 4-6. From Tables 4 to 6, it is clear that the sheet obtained by the present invention is excellent in jet blackness and scratch resistance.
【表４】 [Table 4]
【表５】 [Table 5]
【表６】 [Table 6]
【発明の効果】本発明の樹脂組成物を用いることによ
り、羊毛粉末及び／または羽毛粉末を加えないで用いた
樹脂本来の好適な特性を損なわずにしかも優れた透湿
性、、漆黒性、耐スクッチ性及びドライタッチでスエー
ド調の風合いが付与された成形品を得ることができる。
故に本発明の樹脂組成物は塗料等のコーティング剤とし
て、また成形用基材として合成皮革、人工皮革等の合成
シート、立体成形品、糸等の各種成形品の幅広い用途へ
用いることが可能である。EFFECTS OF THE INVENTION By using the resin composition of the present invention, excellent moisture permeability, jet-blackness, resistance to abrasion, without impairing the preferable characteristics inherent to the resin used without adding wool powder and / or feather powder It is possible to obtain a molded product having a suede-like texture due to the scotch property and dry touch.
Therefore, the resin composition of the present invention can be used as a coating agent for paints and as a molding base material in a wide range of applications such as synthetic leather such as synthetic leather and artificial leather, three-dimensional molded articles, various molded articles such as threads. is there.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成３年６月２１日[Submission date] June 21, 1991
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の詳細な説明[Name of item to be amended] Detailed explanation of the invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【発明の詳細な説明】Detailed Description of the Invention
【産業上の利用分野】本発明は樹脂組成物及びそれを用
いた成形品に係わり、詳しく述べると合成皮革、人工皮
革、透湿性防水布帛等の合成シート、立体成形品、糸等
の成形品の製造に、または塗料等のコーティング剤とし
て用いる際に該合成樹脂の特性を損なわずに、優れた透
湿性、漆黒性、耐スクラッチ性及びドライタッチでスエ
ード調の風合いを付与する有用な樹脂組成物及びそれを
用いた成形品に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition and a molded article using the same, and more specifically, synthetic leather, artificial leather, synthetic sheets such as moisture-permeable waterproof cloth, three-dimensional molded articles, molded articles such as threads. A useful resin composition for imparting a suede-like texture with excellent moisture permeability, jet blackness, scratch resistance and dry touch, without impairing the properties of the synthetic resin when it is used for the production of or as a coating agent for paints and the like. The present invention relates to a product and a molded product using the product.
【従来の技術】合成皮革、人工皮革、金属、プラスチッ
ク、セラミックス、木材等の表面をスエード調触感に仕
上げるための表面処理剤は従来から種々開発されてい
る。代表的なものとしては（１）ポリウレタン樹脂溶液
に脂肪酸エステル、シリカを配合したもの、（２）ポリ
ウレタン樹脂溶液、アクリル樹脂溶液にジメチルポリシ
ロキサン、シリカを配合したもの、（３）ポリウレタン
樹脂溶液にポリエチレン微粉末、ポリブチレン微粉末、
アクリル樹脂微粉末、ウレタン樹脂微粉末、ナイロン樹
脂微粉末あるいはシリコン樹脂微粉末等の１種とシリカ
を配合したもの、等がある。しかし、これらの処理剤で
合成皮革、例えばポリ塩化ビニルレザー（以下、ＰＶＣ
レザーという）や合成樹脂成形品等をグラビアプリンタ
ー法、スプレー法等により表面処理して形成した被覆層
表面は爪で引っかくことにより容易に破壊、変形すると
いう現象が見られ、耐スクラッチ性に欠け、また手で触
れた部分は指紋等が残る、あるいはべた付き感がある等
の問題がある。また、ポリウレタン樹脂、アクリル樹
脂、ナイロン樹脂等の粉体をポリイソシアネート類と共
にウレタン樹脂有機溶媒溶液中で調合し、スプレー処理
する方法も提案されているが、風合い、ポットライフ、
焼付け温度等の問題がある。一方、透湿性を付与する方
法も種々開発されており、代表的なものとしては（４）
ポリウレタン樹脂溶液、ポリアミノ酸ウレタン樹脂溶液
等を用いて多孔質合成シートとする方法、（５）ポリウ
レタン樹脂溶液等にゼラチン微粒子、またはゼラチン微
粒子と微細粉状の革粉を含有させて被膜を形成させ、温
水でゼラチン粒子を一部溶出させる方法（特開平１−２
２２９３８、特開平１−２２２９３９）、等がある。し
かし、（４）の方法については、被膜を極薄状にする必
要があるため耐摩耗性が悪く、またそれ自体において吸
湿機能が小さいため、接触時にべた付き感が生ずるとい
う問題点がある。また、（５）の方法については、工程
が煩雑であり、樹脂に対する分散性が悪く、漆黒性、風
合いがやや劣るという問題点がある。2. Description of the Related Art Various surface treatment agents for finishing the surface of synthetic leather, artificial leather, metal, plastic, ceramics, wood, etc. to a suede-like feel have been developed. Typical examples include (1) polyurethane resin solution mixed with fatty acid ester and silica, (2) polyurethane resin solution, acrylic resin solution mixed with dimethylpolysiloxane, silica, and (3) polyurethane resin solution. Polyethylene fine powder, polybutylene fine powder,
One of acrylic resin fine powder, urethane resin fine powder, nylon resin fine powder, silicon resin fine powder, and the like, and a mixture of silica and the like are available. However, with these treatment agents, synthetic leather such as polyvinyl chloride leather (hereinafter referred to as PVC
There is a phenomenon that the surface of the coating layer formed by surface treatment of leather) and synthetic resin molded products by gravure printer method, spray method, etc. is easily broken and deformed by scratching with nails, and scratch resistance is lacking. Also, there is a problem that fingerprints and the like remain on the part that is touched with the hand, or there is a sticky feeling. In addition, a method of preparing a powder of polyurethane resin, acrylic resin, nylon resin or the like in a urethane resin organic solvent solution together with polyisocyanates and spraying it is also proposed, but the texture, pot life,
There are problems such as baking temperature. On the other hand, various methods for imparting moisture permeability have been developed, and typical methods include (4)
A method of forming a porous synthetic sheet using a polyurethane resin solution, a polyamino acid urethane resin solution, etc. (5) A polyurethane resin solution, etc., containing gelatin fine particles or gelatin fine particles and fine leather powder to form a film , A method in which gelatin particles are partially eluted with warm water (JP-A 1-2)
22938, JP-A-1-222939), and the like. However, with the method (4), there is a problem that abrasion resistance is poor because it is necessary to make the coating film extremely thin, and the moisture absorption function itself is small, so that a sticky feeling occurs at the time of contact. Further, the method (5) has the problems that the process is complicated, the dispersibility in the resin is poor, and the jet-blackness and the texture are slightly inferior.
【発明が解決しようとする課題】本発明は、上述の問題
に鑑みて行われたもので、優れた透湿性、耐スクラッチ
性、および柔らかくドライタッチでべた付き感がなく、
スエード調の風合いを有する分散性のよい合成樹脂組成
物およびこれを加工して得られる成形品を得ることを目
的とするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has excellent moisture permeability, scratch resistance, and softness and dry touch without stickiness.
It is intended to obtain a synthetic resin composition having a suede-like texture and good dispersibility, and a molded article obtained by processing the synthetic resin composition.
【課題を解決するための手段】本発明者は、かかる問題
を解決するために各種合成樹脂について鋭意研究を行っ
た結果、合成樹脂に獣毛粉末及び／または羽毛粉末を含
有させることにより、好適な特性を損なわずに優れた透
湿性、耐スクラッチ性、漆黒性および柔らかくドライタ
ッチでべた付き感がなく、スエード調の風合いを有する
分散性のよい樹脂組成物が得られることを見いだし、本
発明を完成するに至ったものである。即ち、本発明は合
成樹脂１００重量部に対して獣毛粉末及び／または羽毛
粉末を１〜１００重量部含有することを特徴とする樹脂
組成物及び該樹脂組成物からなるまたは該樹脂組成物が
基材にコートされている成形品に関する。以下、本発明
を詳細に説明する。本発明で用いられる樹脂としては種
類を問わずいずれのものでも使用でき、例えばポリアミ
ノ酸、ポリアミノ酸ウレタン、ポリアミド、ポリウレタ
ン、ポリエステル、ポリエステルアミド、アクリロニト
リル系重合体、ポリ塩化ビニル、ポリスチレン及びその
共重合体、ポリビニルアルコール及びその誘導体、ポリ
酢酸ビニル及びその共重合体、ポリアクリルアミドまた
はポリメタクリルアミド及びこれらの誘導体、天然ゴム
及びポリイソプレン、ポリブタジエンなどの合成ゴム並
びにこれらの混合物、ボリエチレン及びその共重合体、
ポリプレン及びその共重合体、フェノール樹脂、メラミ
ン樹脂、尿素樹脂等の１種または２種以上の混合物が挙
げられ、必要に応じて溶剤で希釈して用いることが出来
る。これらの中ではポリウレタン、ポリアミノ酸ウレタ
ン及びポリ塩化ビニルが獣毛粉末及び羽毛粉末の樹脂へ
の分散性及び成形品とした場合の風合い、耐スクラッチ
性等の理由から好ましい。本発明でいう獣毛粉末とは
羊、山羊、兎、ラクダ、アルパカ等の動物より得られる
獣毛（天然ケラチン質繊維）を粉砕したものを意味し、
平均粒径は８０ミクロン以下が好ましく、さらに好まし
くは１０ミクロン以下である。平均粒径が８０ミクロン
より大きいと加工して得られる成形品にざらつき感が生
じ、風合い上好ましくない。本発明でいう羽毛粉末とは
鶏、あひる、がちょう等の家禽、鴨等の水鳥、鳩、ダチ
ョウ等の鳥類より得られる羽毛（天然ケラチン質繊維）
を粉砕したものを意味し、平均粒径は８０ミクロン以下
が好ましく、さらに好ましくは１０ミクロン以下であ
る。平均粒径が８０ミクロンより大きいと加工して得ら
れる成形品にざらつき感が生じ、風合い上好ましくな
い。獣毛粉末および羽毛粉末はそれぞれ単用してもよく
また併用してもよいが、これらの樹脂に対する添加量の
合計は樹脂１００重量部に対して１〜１００重量部、好
ましくは５〜３０重量部である。添加量が１重量部未満
だと透湿性、及びスエード調の風合いが不充分であり、
１００重量部より多いと樹脂に対する分散が困難であ
り、また耐摩耗性、剥離強度、風合い等が低下し好まし
くない。なお、獣毛粉末及び／または羽毛粉末と他のフ
ィラーを併用して樹脂に添加して用いてもなんら差し支
えない。獣毛粉末及び羽毛粉末を樹脂に分散含有させる
方法は用いる樹脂により適宜選択でき、ディスパー分
散、アトマイザー、ダイモミル、ボールミル、三本ロー
ル、万能混合機による混練り等が挙げられる。本発明の
樹脂組成物は成形品の基材として、また塗料、コーティ
ング剤等の用途で用いることができる。本発明の樹脂組
成物からなる成形品は合成シート、、立体成形品、糸等
の形状であり、合成シートとしては合成皮革、人工皮
革、フィルム、板、弾性体等が挙げられる。樹脂組成物
の成形法としては圧縮成形、トランスファー成形、射出
成形、積層成形、押出成形、カレンダー成形等が挙げら
れ、樹脂に応じて適宜選択できる。また、本発明の樹脂
組成物が基材にコートされている成形品の場合の、コー
ティングする成形物に用いることの出来る基材として
は、例えば綿、麻、パルプ、木材、竹、ビスコース人
絹、ベンベルグ人絹、セルロースアセテート等の繊維素
及びその誘導体、絹、羊毛、天然皮革、再生皮革、合成
皮革、人工皮革、ポリアミノ酸、ポリアミノ酸ウレタ
ン、ポリアミド、ポリウレタン、ポリエステル、ポリエ
ステルアミド、アクリロニトリル系重合体、ポリ塩化ビ
ニル、ポリスチレン及びその共重合体、ポリビニルアル
コール及びその誘導体、ポリ酢酸ビニル及びその共重合
体、ポリアクリルアミド及びポリメタクリルアミド並び
にこれらの誘導体、天然ゴム及びポリイソプレン、ポリ
ブタジエン等の合成ゴム並びにこれらの混合物、ポリエ
チレン及びのその共重合体、ポリプロピレン及びその共
重合体、フェノール樹脂、メラミン樹脂、尿素樹脂等の
各種プラスチックス、石英、ガラス、セラミックス、セ
メント類、各種金属類等の１種または２種以上の混合材
が挙げられる。これらの基材による成形品としては、例
えば、布帛、合成皮革、人工皮革、フィルム、紙類、
板、ゴム、プラスチック等のシート状成形品や自動車等
のプラスチック製ハンドル等が挙げられる。また、これ
らの基材による成形品に獣毛粉末及び／または羽毛粉末
を樹脂に添加した本発明の樹脂組成物を塗布による加
工、浸漬による加工、スプレー加工、グラビア加工等を
行うことにより加工することができ、また乾式法で離型
紙上にフィルム化して上記基材とラミネート加工等によ
り表皮材として用いることが出来る。すなわち、加工法
そのものは従来法によることができる。Means for Solving the Problems As a result of earnest studies on various synthetic resins in order to solve the above problems, the present inventors have found that it is preferable that the synthetic resin contains animal hair powder and / or feather powder. It has been found that a resin composition having excellent moisture permeability, scratch resistance, jet blackness, and soft and dry touch without sticking, and having a good dispersibility and having a suede-like texture can be obtained without impairing the characteristics of the present invention. Has been completed. That is, the present invention comprises a resin composition comprising 1 to 100 parts by weight of animal hair powder and / or feather powder with respect to 100 parts by weight of a synthetic resin, and the resin composition or the resin composition. The present invention relates to a molded article coated on a base material. Hereinafter, the present invention will be described in detail. As the resin used in the present invention, any resin can be used regardless of the type, and examples thereof include polyamino acid, polyamino acid urethane, polyamide, polyurethane, polyester, polyesteramide, acrylonitrile polymer, polyvinyl chloride, polystyrene and its copolymerization weight. Polymers, polyvinyl alcohol and derivatives thereof, polyvinyl acetate and copolymers thereof, polyacrylamide or polymethacrylamide and derivatives thereof, natural rubber and synthetic rubbers such as polyisoprene and polybutadiene, and mixtures thereof, polyethylene and copolymers thereof. ,
Examples thereof include one or a mixture of two or more of polyprene and its copolymer, phenol resin, melamine resin, urea resin and the like, and they can be used after diluting with a solvent as necessary. Among these, polyurethane, polyamino acid urethane and polyvinyl chloride are preferable from the viewpoints of dispersibility of animal hair powder and feather powder in resin, texture when formed into a molded product, scratch resistance and the like. The animal hair powder referred to in the present invention means crushed animal hair (natural keratinous fiber) obtained from animals such as sheep, goats, rabbits, camels and alpaca,
The average particle size is preferably 80 microns or less, more preferably 10 microns or less. If the average particle size is larger than 80 microns, the molded product obtained by processing will be rough, which is not preferable in terms of texture. The feather powder referred to in the present invention is a feather (natural keratinous fiber) obtained from poultry such as chickens, ducks, and gooses, water birds such as ducks, birds such as pigeons and ostriches.
Is ground, and the average particle size is preferably 80 microns or less, more preferably 10 microns or less. If the average particle size is larger than 80 microns, the molded product obtained by processing will be rough, which is not preferable in terms of texture. Animal hair powder and feather powder may be used individually or in combination, but the total amount of addition to these resins is 1 to 100 parts by weight, preferably 5 to 30 parts by weight, relative to 100 parts by weight of the resin. It is a department. If the amount added is less than 1 part by weight, moisture permeability and suede-like texture are insufficient,
If it is more than 100 parts by weight, it is difficult to disperse it in the resin, and abrasion resistance, peeling strength, texture and the like are deteriorated, which is not preferable. It should be noted that animal hair powder and / or feather powder and other filler may be used in combination and added to the resin without any problem. The method of dispersing and containing animal hair powder and feather powder in the resin can be appropriately selected depending on the resin used, and examples thereof include disperser dispersion, atomizer, dimmo mill, ball mill, three rolls, and kneading with a universal mixer. The resin composition of the present invention can be used as a base material for molded articles and for applications such as paints and coating agents. The molded product made of the resin composition of the present invention has a shape such as a synthetic sheet, a three-dimensional molded product, and a thread. Examples of the synthetic sheet include synthetic leather, artificial leather, a film, a plate, and an elastic body. Examples of the molding method of the resin composition include compression molding, transfer molding, injection molding, lamination molding, extrusion molding, calender molding, and the like, which can be appropriately selected depending on the resin. Further, in the case of a molded article in which the resin composition of the present invention is coated on a substrate, examples of the substrate that can be used for the molded article to be coated include cotton, hemp, pulp, wood, bamboo, and viscose. Silk, Bemberg silk, fibrin such as cellulose acetate and its derivatives, silk, wool, natural leather, regenerated leather, synthetic leather, artificial leather, polyamino acid, polyamino acid urethane, polyamide, polyurethane, polyester, polyesteramide, acrylonitrile series Synthesis of polymers, polyvinyl chloride, polystyrene and its copolymers, polyvinyl alcohol and its derivatives, polyvinyl acetate and its copolymers, polyacrylamide and polymethacrylamide and their derivatives, natural rubber and polyisoprene, polybutadiene, etc. Rubber and mixtures thereof, polyethylene And their copolymers, polypropylene and their copolymers, various plastics such as phenolic resin, melamine resin, urea resin, quartz, glass, ceramics, cements, various metals and the like, or a mixture of two or more thereof. There are materials. Examples of molded articles made of these base materials include cloth, synthetic leather, artificial leather, films, papers,
Examples include sheet-shaped molded products such as plates, rubber and plastics, and plastic handles such as automobiles. In addition, processing is performed by applying processing, dipping processing, spray processing, gravure processing, etc. to the resin composition of the present invention in which animal hair powder and / or feather powder is added to the resin in a molded product of these base materials. Alternatively, it can be formed into a film on a release paper by a dry method and used as a skin material by laminating with the above base material. That is, the processing method itself can be the conventional method.
【実施例】以下、実施例により本発明をさらに詳しく説
明する。 実施例１ 羊毛粉末の製法 １，１，１−トリクロロエタンにより充分脱脂後の羊毛
をカッターにより数ミリ長のチップとなした脱脂チップ
１ｋｇを０．１Ｎ水酸化ナトリウム水溶液５リットルを
加えて常圧、８ｏ℃にて３０分間撹拌しながら部分加水
分散処理した。これを濾過し、水中に再分散させ、塩酸
溶液で中和、洗浄後、セラミックス製ボールミルにて２
４時間湿式法により微粒子化した。これを遠沈処理後、
乾燥し、平均粒径５〜１０ミクロンの羊毛粉末９００ｇ
を得た。 実施例２ 羽毛粉末の製法 実施例１におけると同様に処理した水鳥（がちょう）の
羽毛チップ１ｋｇを０．１Ｎ水酸化ナトリウム水溶液５
リットルに分散させ、１０リットル容の加圧容器にて１
２０℃で３０分間攪拌しながら部分加水分解した。以
下、再び実施例１におけると同様に処理して平均粒径５
〜１０ミクロンの羽毛微細粉末９２０ｇを得た。 実施例３ ポリウレタン樹脂溶液と羊毛粉末との配合 ポリウレタン樹脂溶液（セイコー化成（株）製「ラック
スキン５００５」）に、その樹脂固形分１００重量部に
実施例１で得た羊毛粉末を５，３０及び１００重量部添
加し、ディスパー撹拌して均一に分散させた後、脱泡を
行い、３種の樹脂組成物Ａ１，Ｂ１及びＣ１を得た。樹
脂組成物Ａ１，Ｂ１及びＣ１における羊毛粉末の分散性
はいずれも良好であった。 実施例４ ポリアミノ酸ウレタン樹脂溶液と羊毛粉末と
の配合 ポリアミノ酸ウレタン樹脂溶液（セイコー化成（株）製
「ラックスキンＡ３５７１」）に、その樹脂固形分１０
０重量部に対して実施例１で得た羊毛粉末を５，３０及
び１００重量部添加し、ディスパー撹拌して均一に分散
させた後、脱泡を行い、樹脂組成物Ｄ１，Ｅ１及びＦ１
を得た。樹脂組成物Ｄ１，Ｅ１及びＦ１における羊毛粉
末の分散性はいずれも良好であった。 実施例５ 塩化ビニル樹脂溶液と羊毛粉末との配合 ポリ塩化ビニル樹脂溶液（セイコー化成（株）製「ラッ
クスキン３０１」）に、その樹脂固形分１００重量部に
対して実施例１で得た羊毛粉末を５，３０及び１００重
量部添加し、３本ロールで均一に分散させた後、脱泡を
行い、樹脂組成物Ｇ１，Ｈ１及びＩ１を得た。樹脂組成
物Ｇ１，Ｈ１及びＩ１における羊毛粉末の分散性はいず
れも良好であった。 実施例６ ポリウレタン樹脂溶液と羽毛粉末との配合 ポリウレタン樹脂溶液（セイコー化成（株）製「ラック
スキン５００５」）に、その樹脂固形分１００重量部に
対して実施例２で得た羽毛粉末を５，３０及び１００重
量部添加し、ディスパー撹拌して均一に分散させた後、
脱泡を行い、樹脂組成物Ａ２，Ｂ２，及びＣ２を得た。
樹脂組成物Ａ２，Ｂ２及びＣ２における羽毛粉末の分散
性はいずれも良好であった。 実施例７ ポリアミノ酸ウレタン樹脂溶液と羽毛粉末と
の配合 ポリアミノ酸ウレタン樹脂溶液（セイコー化成（株）製
「ラックスキンＡ３５７１」）に、その樹脂固形分１０
０重量部に対して実施例２で得た羽毛粉末を５，３０及
び１００重量部添加し、ディスパー撹拌して均一に分散
させた後、脱泡を行い、樹脂組成物Ｄ２，Ｅ２及びＦ２
を得た。樹脂組成物Ｄ２，Ｅ２及びＦ２における羽毛粉
末の分散性はいずれも良好であった。 実施例８ ポリ塩化ビニル樹脂溶液と羽毛粉末との配合 ポリ塩化ビニル樹脂溶液（セイコー化成（株）製「ラッ
クスキン３０１」）に、その樹脂固形分１００重量部に
対して実施例２で得た羽毛粉末を５，３０及び１００重
量部添加し、３本ロールで均一に分散させた後、脱泡を
行い、樹脂組成物Ｇ２，Ｈ２及びＩ２を得た。樹脂組成
物Ｇ２，Ｈ２及びＩ２における羽毛粉末の分散性はいず
れも良好であった。 比較例１ ポリウレタン樹脂溶液とコラーゲン粉末との
配合 ポリウレタン樹脂溶液（セイコー化成（株）製「ラック
スキン５００５」）１００重量部に粉砕したコラーゲン
粉末（昭和電工（株）製「ＣＸ−２４０−１」）を樹脂
固形分に対して５，３０及び１００重量部添加し、３本
ロールで均一に分散させた後、脱泡を行い、樹脂組成物
Ｊ１，Ｋ１及びＬ１を得た。 比較例２ ポリウレタン樹脂溶液とシリカ粉末との配合 ポリウレタン樹脂溶液（セイコー化成（株）製「ラック
スキン５００５」）１００重量部に粉砕したシリカ粉末
（デグサジャパン（株）製「ＯＫ−４１２」）を樹脂固
形分に対して５，３０及び１００重量部添加し、３本ロ
ールで均一に分散させた後、脱泡を行い、樹脂組成物Ｊ
２，Ｋ２及びＬ２を得た。 比較例３ ポリアミノ酸ウレタン樹脂溶液とコラーゲン
粉末との配合 ポリアミノ酸ウレタン樹脂溶液（セイコー化成（株）製
「ラックスキンＡ３５７１」）１００重量部に粉砕した
コラーゲン粉末（昭和電工（株）製「ＣＸ−２４０−
１」）を樹脂固形分に対して５，３０及び１００重量部
添加し、３本ロールで均一に分散させた後、脱泡を行
い、樹脂組成物Ｍ１，Ｎ１，及びＰ１を得た。 比較例４ ポリアミノ酸ウレタン樹脂溶液とシリカ粉末
との配合 ポリアミノ酸ウレタン樹脂溶液（セイコー化成（株）製
「ラックスキンＡ３５７１」）１００重量部に粉砕した
シリカ粉末（デグサジャパン（株）製「ＯＫ−４１
２」）を樹脂固形分に対して５，３０及び１００重量部
添加し、３本ロールで均一に分散させた後、脱泡を行
い、樹脂組成物Ｍ２，Ｎ２及びＰ２を得た。 比較例５ ポリビニル樹脂溶液とコラーゲン粉末との配
合 ポリ塩化ビニル樹脂溶液（セイコー化成（株）製「ラッ
クスキン３０１」）１００重量部に粉砕したコラーゲン
粉末（昭和電工（株）製「ＣＸ一２４０−１」）を樹脂
固形分に対して５，３０及び１００重量部添加し、３本
ロールで均一に分散させた後、脱泡を行い、樹脂組成物
Ｑ１，Ｒ１及びＳ１を得た。 比較例６ ポリ塩化ビニル樹脂溶液とシリカ粉末との配
合 ポリ塩化ビニル樹脂溶液（セイコー化成（株）製「ラッ
クスキン３０１」）１００重量部に粉砕したシリカ粉末
（デグサジャパン（株）製「ＯＫ−４１２」）を樹脂固
形分に対して５，３０及び１００重量部添加し、３本ロ
ールで均一に分散させた後、脱泡を行い、樹脂組成物Ｑ
２，Ｒ２及びＳ２を得た。 検査例１ 透湿度及びスエード調外観の評価 実施例３〜８及び比較例１〜６で得た樹脂組成物及び粉
末無添加の樹脂溶液をそれぞれ離型紙上に溶剤除去後の
厚さが２０ミクロンとなるようにロールコーターで塗布
し、８０℃で５分間、１２０℃で１０分間乾燥して評価
用膜とし、透湿度およびスエード調外観の評価を行っ
た。なお、評価基準は次の通りである。 （１）透湿度 ＪＩＳ Ｌ １０９９（塩化カルシウム
法）に準じた。 （２）スエード調外観 目視により以下の基準で判定し
た。 ○ 天然皮革に酷似している。 △ 天然皮革にやや似ている。 × 天然皮革の感じがない。 結果を表１〜３に示す。表１〜３より、本発明により得
られたシートは透湿度及びスエード調外観ともに優れて
いることは明らかである。EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 Method for producing wool powder 1 kg of defatted chips obtained by cutting the wool sufficiently degreased with 1,1,1-trichloroethane into chips of several millimeters by a cutter, and adding 5 liters of 0.1N sodium hydroxide aqueous solution at normal pressure, A partial hydrolysis-dispersion treatment was performed while stirring at 8 ° C. for 30 minutes. This is filtered, redispersed in water, neutralized with a hydrochloric acid solution, washed, and then 2 with a ceramic ball mill.
Fine particles were formed by a wet method for 4 hours. After centrifuging this,
900 g of dried wool powder with an average particle size of 5-10 microns
Got Example 2 Manufacturing method of feather powder 1 kg of feather tips of waterfowl treated in the same manner as in Example 1 was treated with 0.1N sodium hydroxide aqueous solution 5
Disperse in 1 liter and press in a 10 liter pressurized container to
Partial hydrolysis was carried out with stirring at 20 ° C. for 30 minutes. Thereafter, the same treatment as in Example 1 is performed again to obtain an average particle size of 5
920 g of -10 micron feather fine powder were obtained. Example 3 Blending of Polyurethane Resin Solution and Wool Powder A polyurethane resin solution (“Luck Skin 5005” manufactured by Seiko Kasei Co., Ltd.) was mixed with 5,30 parts of the wool powder obtained in Example 1 in 100 parts by weight of the resin solid content. And 100 parts by weight were added, and the mixture was dispersed by stirring with a disper and then defoamed to obtain three kinds of resin compositions A1, B1 and C1. The dispersibility of the wool powder in each of the resin compositions A1, B1 and C1 was good. Example 4 Blending of Polyamino Acid Urethane Resin Solution and Wool Powder A polyamino acid urethane resin solution (“Lack Skin A3571” manufactured by Seiko Kasei Co., Ltd.) was used, and the resin solid content was 10%.
5, 30 and 100 parts by weight of the wool powder obtained in Example 1 was added to 0 parts by weight, and the mixture was stirred with a disper and uniformly dispersed, followed by defoaming to obtain resin compositions D1, E1 and F1.
Got The dispersibility of the wool powder in each of the resin compositions D1, E1 and F1 was good. Example 5 Blending of Vinyl Chloride Resin Solution and Wool Powder A polyvinyl chloride resin solution (“Lack Skin 301” manufactured by Seiko Kasei Co., Ltd.) was mixed with 100% by weight of the resin solid content of the wool obtained in Example 1. The powder was added in an amount of 5, 30 and 100 parts by weight and uniformly dispersed with a three-roll mill, followed by defoaming to obtain resin compositions G1, H1 and I1. The dispersibility of the wool powder in each of the resin compositions G1, H1 and I1 was good. Example 6 Blending of Polyurethane Resin Solution and Feather Powder A polyurethane resin solution (“Luck Skin 5005” manufactured by Seiko Kasei Co., Ltd.) was mixed with 5 parts of the feather powder obtained in Example 2 per 100 parts by weight of the resin solid content. , 30 and 100 parts by weight were added, and the mixture was dispersed by stirring with a disper,
Defoaming was performed to obtain resin compositions A2, B2, and C2.
The dispersibility of the feather powder in each of the resin compositions A2, B2 and C2 was good. Example 7 Blending of Polyamino Acid Urethane Resin Solution and Feather Powder A polyamino acid urethane resin solution (“Lack Skin A3571” manufactured by Seiko Kasei Co., Ltd.) was used, and the resin solid content was 10%.
5, 30 and 100 parts by weight of the feather powder obtained in Example 2 was added to 0 part by weight, and the mixture was uniformly dispersed by stirring with a disper and then defoamed to obtain resin compositions D2, E2 and F2.
Got The dispersibility of the feather powder in each of the resin compositions D2, E2 and F2 was good. Example 8 Blending of Polyvinyl Chloride Resin Solution and Feather Powder A polyvinyl chloride resin solution (“Luck Skin 301” manufactured by Seiko Kasei KK) was obtained in Example 2 with respect to 100 parts by weight of the resin solid content. Feather powder was added in an amount of 5, 30 and 100 parts by weight and uniformly dispersed by a three-roll mill, followed by defoaming to obtain resin compositions G2, H2 and I2. The dispersibility of the feather powder in each of the resin compositions G2, H2 and I2 was good. Comparative Example 1 Blending of Polyurethane Resin Solution and Collagen Powder Collagen powder pulverized into 100 parts by weight of polyurethane resin solution (“Lackskin 5005” manufactured by Seiko Kasei Co., Ltd. “CX-240-1” manufactured by Showa Denko KK) 5, 30 and 100 parts by weight relative to the resin solid content was added and uniformly dispersed with a three-roll mill, followed by defoaming to obtain resin compositions J1, K1 and L1. Comparative Example 2 Blending of Polyurethane Resin Solution and Silica Powder 100 parts by weight of a polyurethane resin solution (“Luckskin 5005” manufactured by Seiko Kasei Co., Ltd.) was pulverized into silica powder (“OK-412” manufactured by Degussa Japan Co., Ltd.). Resin composition J was added after adding 5, 30 and 100 parts by weight to the resin solid content and uniformly dispersing with a three-roll.
2, K2 and L2 were obtained. Comparative Example 3 Blending of Polyamino Acid Urethane Resin Solution and Collagen Powder Collagen powder pulverized into 100 parts by weight of polyamino acid urethane resin solution (“Luck Skin A3571” manufactured by Seiko Kasei Co., Ltd., “CX-manufactured by Showa Denko KK”) 240-
1 ") was added to the resin solid content in an amount of 5, 30 and 100 parts by weight and uniformly dispersed with a three-roll mill, followed by defoaming to obtain resin compositions M1, N1 and P1. Comparative Example 4 Blending of Polyamino Acid Urethane Resin Solution and Silica Powder Polyamino acid urethane resin solution (“Luckskin A3571” manufactured by Seiko Kasei Co., Ltd.) 100 parts by weight of silica powder (Degussa Japan Co., Ltd. “OK- 41
2 ") was added to the resin solid content in an amount of 5, 30 and 100 parts by weight and uniformly dispersed by a three-roll mill, followed by defoaming to obtain resin compositions M2, N2 and P2. Comparative Example 5 Blending of Polyvinyl Resin Solution and Collagen Powder Collagen powder pulverized into 100 parts by weight of polyvinyl chloride resin solution (“Luck Skin 301” manufactured by Seiko Kasei Co., Ltd., “CX-1240-manufactured by Showa Denko KK”) 1 ") was added to the resin solid content in an amount of 5, 30 and 100 parts by weight and uniformly dispersed by a three-roll mill, followed by defoaming to obtain resin compositions Q1, R1 and S1. Comparative Example 6 Blending of Polyvinyl Chloride Resin Solution and Silica Powder Polyvinyl chloride resin solution (“Luck Skin 301” manufactured by Seiko Kasei Co., Ltd.) 100 parts by weight of silica powder (“OK-” manufactured by Degussa Japan Co., Ltd.) 412 ") is added to the resin solid content in an amount of 5, 30 and 100 parts by weight and uniformly dispersed by a three-roll mill, followed by defoaming to obtain a resin composition Q.
2, R2 and S2 were obtained. Inspection Example 1 Evaluation of Water Vapor Permeability and Suede-Like Appearance The resin compositions obtained in Examples 3 to 8 and Comparative Examples 1 to 6 and the resin solution containing no powder are each 20 μm in thickness after removing the solvent on the release paper. Was coated with a roll coater so as to obtain a film for evaluation by drying at 80 ° C. for 5 minutes and 120 ° C. for 10 minutes, and the moisture permeability and the suede appearance were evaluated. The evaluation criteria are as follows. (1) Water vapor transmission rate According to JIS L 1099 (calcium chloride method). (2) Suede-like appearance The appearance was visually evaluated according to the following criteria. ○ It is very similar to natural leather. △ Slightly similar to natural leather. × There is no feeling of natural leather. The results are shown in Tables 1-3. From Tables 1 to 3, it is clear that the sheet obtained according to the present invention is excellent in both moisture permeability and suede appearance.
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 検査例２ 漆黒性及び耐スクラッチ性の評価 実施例３〜８及び比較例１〜６で得た樹脂組成物及び粉
末無添加の樹脂溶液を黒色ＡＢＳシートにグラビヤプリ
ンターを用いて３０ｇ／ｍ２塗工し、１２０℃で５分間
乾燥して表面仕上げして評価用シートとし、漆黒性乃び
耐スクラッチ性の評価を行った。なお、評価基準は次の
通りである。 （３）漆黒性 目視により以下の基準で判定した。 ○ 黒さが充分である。 △ 黒さがやや欠ける。 × 黒さが欠ける。 （４）耐スクラッチ性 硬度Ｈの鉛筆で表面をこすり、
目視により以下の基準で判定した。 ○ 異常なし。 △ 引きかき傷ややあり。 × 引きかき傷大。 結果を表４〜６に示す。表４〜６より、本発明により得
られたシートは漆黒性及び耐スクラッチ性ともに優れて
いることは明らかである。[Table 3] Inspection Example 2 Evaluation of jet blackness and scratch resistance The resin compositions obtained in Examples 3 to 8 and Comparative Examples 1 to 6 and the resin solution containing no powder were coated on a black ABS sheet at 30 g / m 2 using a gravure printer. The sheet was processed, dried at 120 ° C. for 5 minutes and surface-finished to give a sheet for evaluation, and the jet blackness and scratch resistance were evaluated. The evaluation criteria are as follows. (3) Jetness Blackness was visually evaluated according to the following criteria. ○ Black is sufficient. △ Black is slightly lacking. × Black is missing. (4) Scratch resistance Rubbing the surface with a pencil of hardness H,
It was judged visually by the following criteria. ○ No abnormality. △ Some scratches. × Large scratches. The results are shown in Tables 4-6. From Tables 4 to 6, it is clear that the sheet obtained by the present invention is excellent in jet blackness and scratch resistance.
【表４】 [Table 4]
【表５】 [Table 5]
【表６】 [Table 6]
【発明の効果】本発明の樹脂組成物を用いることによ
り、羊毛粉末及び／または羽毛粉末を加えないで用いた
樹脂本来の好適な特性を損なわずにしかも優れた透湿
性、、漆黒性、耐スクッチ性及びドライタッチでスエー
ド調の風合いが付与された成形品を得ることができる。
故に本発明の樹脂組成物は塗料等のコーティング剤とし
て、また成形用基材として合成皮革、人工皮革等の合成
シート、立体成形品、糸等の各種成形品の幅広い用途へ
用いることが可能である。EFFECTS OF THE INVENTION By using the resin composition of the present invention, excellent moisture permeability, jet-blackness, resistance to abrasion, without impairing the preferable characteristics inherent to the resin used without adding wool powder and / or feather powder It is possible to obtain a molded product having a suede-like texture due to the scotch property and dry touch.
Therefore, the resin composition of the present invention can be used as a coating agent for paints and as a molding base material in a wide range of applications such as synthetic leather such as synthetic leather and artificial leather, three-dimensional molded articles, various molded articles such as threads. is there.
Claims (4)
／または羽毛粉末を１〜１００重量部含有することを特
徴とする樹脂組成物。1. A resin composition comprising 1 to 100 parts by weight of animal hair powder and / or feather powder with respect to 100 parts by weight of resin.
１０ミクロン以下であることを特徴とする請求項１記載
の樹脂組成物。2. The resin composition according to claim 1, wherein the animal hair powder and the feather powder have an average particle diameter of 10 μm or less.
レタン及びポリ塩化ビニールから選ばれる１種以上の樹
脂が主体であることを特徴とする請求項１または２記載
の樹脂組成物。3. The resin composition according to claim 1, wherein the resin is mainly one or more resins selected from polyurethane, polyamino acid urethane and polyvinyl chloride.
成物からなる、または該樹脂組成物が基材にコートされ
ている成形品。4. A molded article comprising the resin composition according to claim 1, or a base material coated with the resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12566091A JPH05222293A (en) | 1991-03-11 | 1991-03-11 | Resin composition and molding produced therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12566091A JPH05222293A (en) | 1991-03-11 | 1991-03-11 | Resin composition and molding produced therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05222293A true JPH05222293A (en) | 1993-08-31 |
Family
ID=14915503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12566091A Pending JPH05222293A (en) | 1991-03-11 | 1991-03-11 | Resin composition and molding produced therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05222293A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021002762A1 (en) * | 2019-07-03 | 2021-01-07 | Peter John Crone | Fire-retardant composite materials |
-
1991
- 1991-03-11 JP JP12566091A patent/JPH05222293A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021002762A1 (en) * | 2019-07-03 | 2021-01-07 | Peter John Crone | Fire-retardant composite materials |
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